Method of making beta-amino sulfonic compounds



Patented june s, 1950 UNITED STATES PATENT oFFice Ms'rnon or maxmo p-xmmo sunromc comcuups Marvin a. Gold, Chicago, 111., asainor to The Viskin: Corporation, Chicago, 111., a corporation of Virginia No Drawing. Application September 21, 1945, Serial No. 617,929

(CL zoos-s13) ll Claims.

- v H R; NO r-- -80!" wherein R1 represents hydrogen, alkyl, aryl, halogen, alkoxy or aryloxy group, R1 represents hydrogen, alkyl, aryl, halogen,

alkoxy or arylo'xy group, Ra represents hydrogen, alkyl, aryl, halogen,

alkoxy or aryloxy gr p. and M represents hydrogen, a metallic ion, ammonium or substituted ammonium ion.

The salts of fl-nitro sulfonic acids are obtained according toone phase of this invention by reacting the selected-nitro olefin with an alkali metal, ammonium or Nsubstituted ammonium bisulfite. In the process generally the selected; olefin as such or in an appropriate solvent is added to an' aqueous solution of the selected bisulfite. The bi- 2 temperature. Nitro olefins of low molecular w i ht react with bisulflfi at slower temperature thanthose of higher molecular'weight'; Though in the preferred operation ofthe process-the re-.. action was carried out at a temperature or .irom C. to 60 0., itJs to :be understood. however, that. temperatures higher than 60 C lower than m 1:. can also be f The-nitro olefin which constitutes one of the reactants can be represented by the following general'iormula:

sulfite addsto the nitro olefin as by the following equation illustrating the reaction which takes place when nitroethylene is added to an aqueous solution of ammonium bisulfite:

As is indicated by the above equation. theoretically 1 mol of bisulfite reacts with 1 mol of nitro olefin. In practice, however, a slight excess of bisulfite is utilized, though, of course, the reactantsmay be used in the theoretical amount required for the reaction or the nitro olefin may be used in excess or the theoretical amount required for the reaction.

The reaction is generally exothermic and requires external cooling to maintain it at optimum R1 v represents hydrogen. alhyl, aryl, halogen,

alkoxy or aryloxy group, B=XP d k alkoxy oraryloiw srbiinand R1 --represents hydroganigalk yl, ai'yL v halogen,

alkoxy or aryl'oxy group."

As illustrative specific nitro olefins which can be used in the process are the following:

2-nitro-l-butene' 2-phenyl-1-nitroethylene l-nitropropene z-nitropropene Nitroethylene l-phenyl-l-nitroethylene l-phenyl-l-nitropropene I-naphthyI-l-nitroethykne i-naphthyl-l-nitropropene z-naphthyl-i-mtro rogene l-chloro-l-nitroethylene l-chloro-l -nitropropene' l-methoxy-l-nitroethylehe l-methoxy-z-nitroethyl'ene 2-methoxy-2-phenyl-1-nitroethylene 2-phenoxy-1-nitroethylene In place of the nitro olefins, nitro cyclo compounds, such as l-nitrocyclohexene and z-methyil-nitrocyclohexene, can be used as one or the reactants.

As previously mentioned, the bisulfite which is utilized in the process'can be an alkali metal, ammonium, or N-substituted ammonium bfisulfite. Sodium bisulfite and potassium bisulfite are ilaryl, halogen.

lustrative examples oi alkali metal bisulfites which can be used in the process. Bisulfltes of the following N-substituted ammonium ions are illustrative examples of specific N-substituted ammonium bisulfltes which can be used in the process:

The previously described process produces an alkali metal, ammonium, or N-substituted ammonium salt of fl-nitro sulfonic acid. Such a. salt can, in accordance with another phase of this invention, be converted to the corresponding free nitro sulfonic acid or a salt containing any desired cation. I

The free nitro sulfonic acid is prepared, in general, from the bisulfite addition product by ion exchange using any of the well-known ion exchange procedures and materials, such as, for example, a certain exchange resin. Thus, by passing a salt of the nitro sulfonic acid through a column of an acid form of cation exchange resin, an aqueous solution of the free nitro sulfonic acid is obtained. The solution of the free nitro sulfonic acid can be concentrated or diluted as desired by the appropriate removal or addition of water. If desired, the free sulfonic acid can be removed from solution in any appropriate manner.

When a salt having a cation other than that obtained by the hereinbefore described bisulfite addition process is desired, such salt can be obtained by appropriate reaction of the free nitrosulfonic acid and a compound containing the desired cation. In one embodiment of this form of the invention, the aqueous solution of the free nitro sulfonic acid obtained from a column of a cation exchange resin with or without dilution or concentration as desired is treated with an equivalent quantity of an oxide, hydroxide, or carbonate of any desired cation or substituted ammonia. The salts are obtained by evaporation of the water and are purified by recrystallization from appropriate solvents.

Alternatively, a solution of a bisulfite addition product can be passed over a cation exchange resin which has been converted to the desired cation form. The resulting aqueous eiiluent contains the new cation salt of the nitro sulfonic acids.

The ,B-nitro sulfonic acids or their salts can also, in accordance with another phase of this invention, be converted to the corresponding 3- amino sulfonic acids. According to this phase of the invention, the hereinbefore mentioned 3- nitro sulfonic acids or salts thereof are reduced to the corresponding amino sulfonic acid.

The precise fl-amino sulfonic acid obtained depends on the p-nitro sulfonic acid or salt thereof reduced. In general, the p-amino sulfonic acid which can be obtained can be represented by the following general formula:

wherein I R1 represents hydrogen, alkyl, aryl, alkoxy or aryloxy group,

R2 represents hydrogen, alkyl, aryl, alkoxy or aryloxy group, and

R3 represents hydrogen, alkyl, aryl, alkoxy or aryloxy group.

Preferably, the reduction is carried out by either an iron reduction in aqueous solution or by hydrogenization using a,catalytic agent, such as nickel, although other known reducing procedures can be used.

The manner and details for practicing the invention will become more apparent from the specific examples hereinafter set forth, it being understood that the invention. is not restricted to such specific examples which are set forth as illustrative embodiments only. In the examples, the proportions are parts by weight, and the temperatures are the uncorrected centigrade thermometer readings.

PREPARATION OF SALTS OF -NITRO SUL- FONIC ACIDS Example 1 To a well-stirred solution of 538 parts of a 43% aqueous ammonium bisulfite solution initially brought to 30 was added 226 parts of 2-nitro-1- butene over a period of fifteen minutes. By external cooling, the reaction temperature was kept between 35- 40. The crystalline product separated as the reaction proceeded. When addition was complete, stirring was continued while the temperature was kept between 35-40 for thirty minutes longer. Then the reaction mixture was cooled to 10 and the product separated by filtration. The filtrate was concentrated and additional quantities of the product were recovered by crystallization therefrom to give a final yield of 88% of ammonium-2-nitrobutanel-sulfonate. A sample purified for analysis by crystallization from methanol melted with decomposition at 203-206.

Example 2 To a well-stirred solution of 23.2 parts of a 43% aqueous ammonium bisulfite solution warmed to 40 was added a solution of 15 parts 2-phenyl-1-nitroethylene in 15 parts dioxan over a period of about five minutes while keeping the reaction temperature at 40-by external cooling. After stirring the reaction mass, while the temperature was maintained at 40, thirty minutes longer, the mixture was cooled by means of an ice-bath, thereby causing crystallization of the reaction product. The crystallized product was removed by filtration. The additional reaction product was isolated in a similar manner after concentrating the filtrate under reduced pressure. The desired product was then separated from inorganic material by taking up in hot ethanol. Upon the addition of benzene and allowing the material to crystallize slowly, 20 parts yield) of ammonium-Z-nitro-1-phenyl ethane-l-sulfonate was obtained, melting with decomposition at -174. This material was found to have two melting points. Upon rapid crystallization from concentrated ethanolic solutions, a low melting form could often be obtained. Either form is convertible to the other by seeding 7 or the mode of crystallization. The purified materlals had the melting points of 130-131 and 170-171 with decomposition.

Example 3 To a well-stirred solution of .550 parts of a 43% aqueous ammonium bisuliite solution warmed to 30 was added 198 parts of l-nitropropene over a period 01 thirty minutes while the reaction temperature was kept between 35-40 by external cooling. After the addition was complete, stirring was continued, while the temperature was kept between 35-40, for an additional thirty minutes. The resulting clear solution was concentrated under reduced pressure to a thick viscous oil. This was taken up in hot ethanol, leaving behind a small amount of inorganic bisulfite. Upon the addition of methyl isobutyl ketone and cooling in arefrigerator to a temperature of 5, a total of 350 parts (in three crops), corresponding to 83% yield of ammonium-l-nitropropane-2-sulfonate, was obtained. The purified product, after several recrystallizations from ethanol-methyl isobutyl ketone mixtures, melted at 141-143.

This product is of a soft waxy crystalline nature and appears to form solid gels with solvents such as benzene and various ketones.

Example 4 To a well-stirred solution of 200 parts of a 43% aqueous ammonium bisulfite solution was added 72.6 parts of 2-nitropropene over a period of fifteen minutes. The reaction temperature was kept between 3040 by external cooling. Stirring was continued for an additional thirty minutes at room temperature. Then the reac tion mixture was cooled to and the crystalline product was separated by filtration. Some additional material was obtained by crystallization at 10 from thefiltrate after inorganic salts precipitated with methanol were removed and the filtrate concentrated under reduced pressure. A total yield of 135 parts (87% yield) of ammonium-Z-nitro-propane-l-sulfonate was recovered in this manner. The product purified for analysis by recrystallization from methanol melted with decomposition at 190-191.

Example 5 To a well-stirred solution of 125 parts of a 43% aqueous ammonium bisulfite solution held at -20 was added 38 parts of pure nitroethylene over a period of thirty minutes. Stirring was then continued at room temperature for an additional inin utea' At the end oi this period the reaction mixture was cooled to 5'' and the crystalline "product separated by filtration.

The filtrate was concentrated and some addi- 5 tional product was obtainedthereifrom by crystallization at 5. to'glve a total yield of 89.5 parts or 70% of ammonium-2-nitroethane-l-sulfonate. A sample purified for analysis by recrystallizationsfrom ethanol melted with decomposition at 191. -192.

PREPARATION 01"" fl-NITRQO SULFONIC ACID ANDSALTS THEREOF Example 6 A glass column filled with Zeo Karb cation exchange resin was treatedwlth a 4% aqueous solution of hydrochloric acid to convert the resin to the acid form. Then excess acid was removed by washing the column with distilled water until no more chloride ion could be detected in the effluent. Next a solution of 50 g. of ammonium- 2-nitro butane-l-sulfonate in 1250 cc. distilled water was passed through the column. The exchange was completed by washing with distilled water until the effluent no longer gave a test for acidity. The combined efliuent contained the free 2-nitrobutane-1-sulfonic acid. It was measured and an aliquot portion titratedfor acidity. The selected amine, oxide, hydroxide or carbonate in equivalent quantity was reacted with the solution and, upon evaporation of the mixture, the corresponding salt of the nitro sulfonic acid was obtained. Several illustrative salts and their analyses obtained in thisprocedure are listed in the Table I" hereinafter set forth.

PREPARATION OF SALTS OFp-NITRO SULFONIC ACID BY ION EXCHANGE Example 7 The column of a. Zeo Karb ion exchange resin was saturated with a dilute aqueous solution containing 3%-5% of sodium chloride. Then after washing the column thoroughly with distilled water, a 4% solution of ammonium-Z-nitrobutane-l-sulfonate was passed through. The eilluent and washings were concentrated on the steam bath to give sodium-2-nitrobutane1- sulfonate, which is identical with the product obtained by the procedure of Example 6 when sodium carbonate or hydroxide was reacted with the free acid.

The properties of the products of Examples l-7 inclusive are set forth in the following 55 table:

TABLE I.-SALTS OF fl-NITRO SULFONIC ACIDS Per Cent Cation Per Cent Nitrogen Per Cent Sulfur Example Formula M. P., "0.

Found Theory Found Theory Found Theory 1. C:HsCH(NO:) CH1SO$NH4 KB-m6: dec-.. 13. 51 13. 99 16. 03 15. 91 2.- cmcmsomnccnmo. {eggs- 11. 20 11.29 12. 12.90 3. CHaCH(SO;NH CHzNOa Lil-143 14. 57 15. O5 17. 43 17 22 4.. CHQCH(NO2)CHISO3NHI -131 dec... 14. 46 15. 05 17.04 17 22 5. Noiomomsomni I6. 20 l6. 2a 19. 11 18.63

CzHsCH Oz) CHrSOgNL- 11. 0 l1. 2 15. l5 l5. 6 CIHICH NO:)CH:SO:K l7. 6 l7. 7 l4. 1 l4. 5 (CxHsC (NO|)CH:S03)!B8-- 27. 5 27. 4 l0. 3 10. 0 (CiHiCPHN O1)CHiSO;)iCa. 300 9. 94 9. 9 7. 22 6.95 15.55 15. 85 C,HiCH(N 090111809100 13. 33 13. 9 6. 26 6. 62

11150110 0:)CHzSOzTl 3. 54 -3. 62 8. 25 8. C:HsCH(NOz) OHISO! Brucine 7. 64 7. 27 5. 56 5. 58 2C|HtCH(NOz)CH:SOi):Pb 37 l 36. 2 4. 38 4. 9

C HaCHQN 0;)CH1S093Z111' l68l72 dec... 14. 6 15. l 13. 9 14. 9

The lead salt does not ve a sharp analysis as it was contaminated by a polymeric lead salt, which could not be removed completeiltv after many recrysta izations.

he zinc salt was diificult to purify due to its extreme tendency toward coordination with most crystallization solvents.

Example 8 v -In a reaction vessel fitted with efllcient stirrer 8 charcoal, the solution was concentrated and a little ethyl alcohol added. The resulting 2-amlnopropane-l-sulfonic acid, after several recrystallizations, melted at 318-320 with decomposition. and reflux condenser were placed 12 parts of iron 5 Example 11 1 filings and 55 parts of water. Then with rapid In a Suitable reaction vessel were placed 35 agitation was added 0.5 part concentrated hyparts of iron filings and 75 parts or waten vigob drochloric acid. The. mixture was heated to reous agitation was employed and 1 part of concem flux and then 8 parts of ammomum'lmtro 10 trated hydrochloric acid was added. After five propane'z'sulfmate in 159M175 l was minutes of stirring, 50 parts of ammonium-2- added dropwise- The reaction was t and nitrobutane-l-sulfonate was added, followed by refluxed for four hours. Then the precipitated 75 parts more of water. The mixture was gram iron oxides were removed by filtration of the hot uauy heated to reflux and then 16 parts concem solution. The filtrate was then made slightly hated hydrochloric acid in 20 parts of water alkaline with ammonium hydroxide and a little added dropwise over a period of twenty minutes hydrogen peroxide added o oxidize fenous ions After continued stirring and refluxing I01 one to ferric. After stirring with a. little charcoal hour the hot mixture was mterei The precmb and filteTmgthe inmate was evaporated to tated iron oxides were washed with warm water. small volume. Addition of ethyl alcohol caused 20 The combined filtrate and washings were made the 9 custamzation 9 basic with ammonia and treated with a little hysulfonic a1c1d. Recrystallization from aqu drogen peroxide. Then after clarifying the solugave a pfloduct meltmg Wlth decompo' tion with charcoal, it was concentrated to a small sition at 283-286 volume and allowed to crystallize. The resulting Example 9 Z-amino-butane-l-sulfonic acid, after several re- In a suitable reaction vessel were placed 92 ggfii g sg gggrgggl water melted wlth decomparts of iron filings and 150 parts of water. The mixture was vigorously stirred and 1.5 parts of Example 12 concentrated hydrochloric acid was added. After A mlXture 0f 20 Parts Of flumofive minutes 172 parts of ammOnium-Z-nitmbutane1-sulfonate, 100 parts of distilled water, ethane-l-sulfonate and 50 parts more of water a 3 pa of Ra y i k l cataly t was placed were added. The reaction mixture was slowly in a hydrogenation bombh mb was s aled heated to reflux over a period of fifteen minutes. and filled With hydrogen to pressure 01 1200 Then a solution of 50 parts concentrated hydropounds- Then Shaking W ta t a d the bomb chloric acid in 50 parts of water was added dropheated After two hours at this wise with continued reflux over a period of peratule er was no longer any drop in pressure. thirty-five minutes. After refluxing and stirring The m was cooled. p d, and the solution for an additional hour, the reaction mixture was filtered from the nickel catalyst T i e was clarified with charcoal and evaporated to a small concefitl'ated and allowfid crystalllzer v l volume. Upon addition of ethyl alcohol, the dez-ammoblltane-l-sulfomc 801d. de tical with sired Z-aminoethane-l-sulfonic acid crystallized that Obtained by iron reduction in Example from solution. Several recrystallizations from Example 13 aquemls ethyl alcohol gave a Product flecompos In a suitable reaction vessel were placed 50 ing A mixed melting Point Wlth parts of iron filings and 100 parts of water. The thentic sample of taurine gave no lowering 1n mixture was ti red vigorously and 1 part of bymelting Point drochloric acid was added. Then heat was ap- Ewample 10 plied and the reaction brought to the reflux tem- In a suitable reaction vessel were placed 42 perature. At this point, a solution of 15 parts of parts of iron filings and parts of water. Vigor- 50 ammonium-2-nitro-l-phenylethane-l sulfonate ous agitation was employed and 1 part of conin 50 parts of water was dropped in over a period centrated hydrochloric acid was added. After of fifteen minutes. Then the reaction was stirred five minutes a solution of 62 parts of ammoniumunder reflux for three hours. At the end of this 2-nitropropane-l-sulfonate in 50 parts of water period the hot mixture was filtered. The filtrate was added. The reaction mixture was then gradwas made basic with ammonia and then oxidized ually heated to reflux. At the point of reflux, a with a little hydrogen peroxide. Then after clarisolution of 23 parts hydrochloric acid in 50 parts fying with charcoal, the solution was concenof water was added dropwise over a period of trated and a little methanol added. The 2-amithirty minutes, after which reflux was continued no-l-phenylethane-l-sulfonic acid crystallized in to the end of an hour. The hot solution .was filwhite platelets. Recrystallization from aqueous tered and the precipitated iron oxide was washed methanol gave a product melting at 379 with dewith water. The combined washings were made composition. basic with ammonia and treated with a little hy- The properties of the products of Examples drogen peroxide. Then after clarification with 8-13 inclusive are set forth in the following table:

TABLE lI.AMlNO ,SULFONIC ACIDS Per Cent Per Cent l ur l i m d Per Cent ggfgg Example Formula M. P., C. Sulfur Nitrogen Theory Theory I 11 I II NHzCHzOHzSOaH 310 dec 25. 62 25.48 25.44 11.20 11.00 11.34 Nmcnwrmomsomnn 31s-s20 21.03 23.04 21.00 10.06 10.14 9.8:; NHzCHgCH(CH )S03H 2s3-2s0 dec 23. 02 22.95 22.23 10.00 9.13 11-12-... NHzCH(CzH5)CHgS03Hr-- 30a300 dec. 20.93 20.10 20.10 9.14 9.05 9.04 NH2CHzCH(C0H5)SO;H-.- 319 dec 15. 02 15.20 10.05 0.01 1.20 1.01

It is to be understood that the foregoing data of Tables I and II were obtained from single prep-.

The Zeo Karb cation resinutilized in Examples 6 and 7 (product of Permutit Company) consists essentially of a sulfonated coal. Obviously, the invention is not restricted to such specific ion exchange resin and that other of the known appropriate ion exchange resins or saltscan be used. The embodiment of the invention set forth in Example 7 is particularly suitable for monovalent cations, such as sodium, potassium, lithium, thallium, substituted ammonias, etc.

The ammonium salts of the nitro sulfonic acids are neutral salts,'and, as shown Ln Examples 8-13 inclusive, such salts can be reduced to the corresponding amino compounds. The amino group is a basic group and, during the process of producing the same, produces an internal salt with the sulfonic radical which liberates free ammonia. The free ammonia is either vaporized out of the reaction mixture or neutralized by the addition of an acid, such as hydrochloric. the cation of the salt of the nitro sulfonic acid undergoing reduction is a metal, an acid is added, as the reaction proceeds, to neutralize the metal hydroxide produced and form a neutral salt thereof. For example, if a calcium salt of the nitro sulfonic acid were reduced, an acid would be added, as the reaction proceeds, to neutralize the calcium hydroxide and form a neutral calcium salt.

In the method of reducing the salts of the nitro sulfonic acids, wherein the reduction is obtained through the use of iron, ferrous ions are produced. Ferric hydroxide is less soluble than ferrous hydroxide. Consequently, after the reduction operation all the iron is converted to the ferric state in order that it may be precipitated more completely and removed from the solution.

Any appropriate oxidizing agent to convert the ferrous'ions to ferric ions can be used. Air may constitute such an oxidizing agent and when used it can be bubbled through the reaction medium. However, hydrogen peroxide is the preferred oxidizing agent since its action is faster and does not introduce any additional ions which might complicate the isolation of a pure product.

The use of charcoal in Examples 8-13 is not critical. It is used for the purpose of clarifying the reaction mixture when a pure while crystallized product is desired.

The instant invention provides nitro sulfonic acids and salts thereof which have not been previously known or described, and also new and effective processes for the production of such acids and salts.

The nitro sulfonic acids and salts thereof are useful as intermediates for chemical synthesis, and also, in certain cases, may find uses as wetting, detergent or emulsifying agents.

The simplest p-amino sulfonic acid is known as taurine, which has been obtained by hydrolysis of taurocholic acid, and which has been found useful in the preparation of wetting, detergent and emulsifying agents. However, the major deterrent to its wider use has been its relatively high price.

The reduction of the new nitro sulfonic acids When l0 and salts thereof to the corresponding p-amino sulfonic acids provides a new procedure for the production of taurine and taurine-homologues by a relatively simple and cheap procedure.

Since it is obvious that various changes and modifications may be made in the above description without departing from the nature or spirit thereof, this invention is not resricted thereto except as set forth in the appended claims.

I claim:

1. A process for the preparation of aliphatic p-amino sulfonic acids, which comprises reacting salts of aliphatic p-nitro sulfonic acids with hydrogen.

2. A process for the preparation of aliphatic p-amino sulfonic acids, which comprises reacting the ammonium salt of an aliphatic p-nitro sulfonic acid with hydrogen.

3. A process for the preparation of an aliphatic p-amino sulfonic acid, which comprises reducing the ammonium salt of an aliphatic p-nitro sulfonic acid by iron reduction,removing the liberated ammonia from the reaction mixture, filtering the reaction mixture, converting the ferrous ions produced in the reaction to ferric ions, removing said ferric ions from the solution, and thereafter sepa rating the aliphatic p-amino sulfonic acid from said solution.

4. A process for the preparation of an aliphatic p-amino sulfonic acid, which comprises treating an aqueous solution of an ammonium salt of an aliphatic p-nitro sulfonic acid with hydrogen in the presence of a nickel catalyst, and separating the aliphatic fl-amino sulfonic acid from the reaction mixture.

5. A process forthe preparation of 2-aminobutane-l-sulfonic acid, which comprises reducing ammonium-2-nitro-butane-l-sulfonate by iron reduction, removing the liberated ammonia from the reaction mixture, filtering the reaction mixture, converting the ferrous ions produced in the reaction to ferric ions, removing said ferric ions from the solution, and thereafter separating the f-amino-butane-l-sulfonic acid from said soluion.

6. A process for the preparation of 2-aminoethane sulfonic acid which comprises reducing ammonium-2-nitroethane-1-sulfonate with hydrogen.

'1. A process for the preparation of 2-aminopropane-l-sulfonic acid which comprises reducing ammonium-2-nitropropane-l-sulfonate with hydrogen. I

8. A process for the preparation of 2-aminobutane-l-sulfonic acid which comprises reducing ammonium-2-nitrobutane-l-sulfonate with hydrogen.

9. A process for the preparation of aliphatic p-amino sulfonic acids which comprises reducing a salt of a p-nitro aliphatic sulfonic acid by iron reduction, converting the ferrous ionsto ferric ions, removing said ferric ions from the solution and thereafter separating the aliphatic B-amino sulfonic acid from said solution.

10. A process as set forth in claim 9 wherein the cation of the salt of the p-nitro aliphatic sulfonic acid is a metal and an acid is added as the reaction proceeds to neutralize the hydroxide of said metal produced.

MARVIN H. GOLD.

(References on following page) 11 12 nmmcns crrm Number Name D t The lollowmg references are of record in the 23533" Von 51"! NW- 4 tile 0! this patent: .808 Heeth et a 1hr. 29, 1949 um'mn STATES mm 5 FOREIGN m'rm'rs Number Name Date Number Country Date 409,999 Andreaen June 29, 1999 805.093 I'm-nee Nov. 10, 1996 991,192 Geneahelm Jan. 14, 1902 571,15! Greet Br! 1949 1,999,492 mach Apr. so, 1995 2,109,919 um- Dec. 29. 1999 10 Mum-Rm 2,170,390 nomen Aug. 22, 1939 chemlcfl DP- 394 to 2,191,990

Harrie D 5 19 399 (1949). 

1. A PROCESS FOR THE PREPARATION OF ALIPHATIC A-AMINO SULFONIC ACIDS, WHICH COMPRISES REACTING SALTS OF ALIPHATIC B-NITRO SULFONIC ACIDS WITH HYDROGEN. 